Azo dyes



atented Mar. 11, 1930 srArss RICHARD ST'USSER, OF COLOGNE-DEUTZ, GERMANY, ASSIGNOR TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE AZO DYES No Drawing. Application filed April 7, 1928, Serial No. 268,378, and in Germany April 21, 1927.

I The present invention relates to new azodyestutl's of the probable general formula:

wherein X represents a sulfur or oxygen CODE wherein X, 3/ and a are to be explained as mentioned above; or 'two similar or dissimilar moleculesot compounds of the probable general formula:

- COOI'I \vl1e1ein u represents any desired coupling component, g stands for a group of the kind NH R-a-, wherein It represents an aromatic'nucleus and a represents one of the groups and SO which are caused to be reacted upon by one molecule of phosgene or thiophosgene; or the compound of the foris diazotized, coupled with any desired azo component, reduced, caused to be reacted upon b a compound of the generalformula: NO fi-b, wherein R represents an aromatic nucleus and 6 stands for COCl or SO CI, reduced and then treated with phosgene or thiophosgene. T

The dyestuffs thus obtainable may be symmetrical or unsymmetrical ones.

I have found that the symmetrical dyestuffs of these series, especially such ones as contain sulfo-groups in the coupling component and wherein the X mentioned'in the first formula stands for O and the group NHRa means -NHRC(), are in many cases of especially high technical value, but it is to be understood that all the dyestuffs as described possess valuable technical properties and in particular have the advantage that the dyeings obtainable by means of them exhibit an increased fastness to water and washing after treatment on the fibre with suitable metal salts. Besides the shade of the dyeings tends by this after-treatmenttowards yellow or red with the result that an eficnded range of colors becomes availa e.

As for the rest the products described above are yellow to black powders sparingly soluble in the usual organic solvents, soluble in concentrated sulfuric acid withyellow to blue colorations, yielding on treatment with stannous chloride and hydrochloride acid among other products 52.5-diaminobenzene1-carboxylic acid.

The following; examples illustrate my in vention without limiting it thereto, the parts being by weight:

Exmnple J.182 parts of.fi-nitro-Q aminobenzoic acid are diazotized in water with 69 parts of sodium nitrite and 400 parts of hydrochloric acid of 195 B., and coupled with 287 parts of acetoacetic acid ortho anisidide sulfonic acid dissolved in a solution 5 rendered alkaline by means of sodium car- 0 out and filtered.

bonate. 720 parts of crystallized sodium sulfide are then added and stirred'with gentle heating until the reduction of the nitro group is complete. The aminoazo dyestufi is salted Thereupon it is re-dissolved in water and condensed with 1netanitro-benzoyl chloride ,at about 45 C. in the presence'of sodium acetate, until the free amino group has disappeared. After rendering the solution alkaline with sodium carbonate, the dyestuff is salted out and filtered. It is re-dissolved in hot water and reduced at about 60 C. with 7520 parts of crystallized sodium sulfide. \Vhen the reduction is complete the dyestuif is separated by salting out and filtered. The dyestuff is then redissolved in water and converted into the urea or thiourea compound by the treatment at about 45 C.- with phosgene or thiophosgene in the presence of sodium acetate, filtered and dried.

Thenew 'dyestufl having in its free state the following formula:

soar! o ooNHQN=N- br 50 NHO coon J: o=o

' CH NHQ coon 0. CONH N=Ni 1 I O NH appears as a yellow powder, which dyes unmordanted cotton yellow. After-treatment with metallic'salt s, .in particular :with copper salts yields a greenish yellow, fast to water, washing and light.

E wam'ple 2 .-182 parts of 2-a1nino-5-nitrobenzenel-carboxylic acid are diazotized in the known -manner and coupled with 254 parts of 1-para-sulfo-phenyl-3-methyl-5-pyrazolone, dissolved in the presence of acetic acid. The solution is then rendered alkaline with sodium carbonate, and the nitroazo dyestutl' is reduced to the aminoazo dyestufl' by means of 720 parts of crystallized sodium SOIH CONH

. AOIH and appears as a yellowish brown powder which dyes unmgrdanted cotton orange. By after treatment with coppersalts, a brownish yellow is obtained, fast to washing and light. The dyestufl' yields, when reduced with stannous chloride and hydrochloric acid, 2.5-diamino-benzene-l-carboxylio acid, S-aminobenzene-Lcarboxylic acid and l-p-sulfophenyl-3-methyl-4-aminio-fi-pyrazolone.

Emample 3. The azo dyestuffs, obtained in the known manner from 182 parts of 2-amino-5-nitro-benzene-l-carboxylic.acid and 306 parts of 6-sulfo-1-,8-naphthyl-S methyl-5- pyrazolone, is reduced by means of720 parts of crystallized sodium sulfide in 200 parts of caustic soda solution of 38 B. and condensed .Wlth 3-nitro-4-methoxy-benzoic acid chloride. The condensation product is re- "di'iced by means of 720 parts of crystallized sodium sulfide, and the reduction product is converted in the known manner into the urea compound.

intone? The dyestufi thus obtained having in its freestate the following formula:

i of crystallized sodium sulfide and condensed With meta-nitro-henzoyl chloride, then reduced to the aminobenzoylaminoazo dyestuff by means of 720 parts of crystallized sodium sulfide and converted into the urea compound having in its free state the following formula:

In this manner a dyestufi is ohtainedwhich' dyes unmordanted cotton a blueish red. By after treatment of the dyeing with copper salts a Bordeaux red is obtained, fast to Washing and light.

Ezvample 5. -'l[he meta-aminobenzoylaminoazo dyestuff' obtained as described in Example 4: is condensed with 3-nitro-lmethoxy-benzoic acid'chloride, until the free amino group oan no longer be detected. The condensation ductis reduced by means of 720 parts of crystallized sodium sulfide and the 3amino-4-InethoXyhenzoyl-mcta-aminobenzoylaminoazo dyestulf is then converted in the known manner into the urea compound having in its free state the following, formula:

, v on CO-NHQN= (JO-NEG 00H NH one:

0 0 0 a OCHa coon 0H slouz In this manner also a dyestuif is obtained, which dyes unmordanted cotton a bluish red. On aftertreatment with copper salts the dyein becomes a Bordeaux red.

iwample 6.'-The dyestuff obtained from 182 parts of diazotized 2-amino-5-nitro-benzene-l-carboxylic acid and 348 parts of 1- ethoxy-8-hydroxy-naphthalene-3.6-disulfonic acid is reduced to the aminoazo dyestufl' by means of 720 parts of crystallized sodium sulfide and condensed with meta-nitrobenzoyl chloride until the free amino group can no longer be detected. The meta-nitrobenzoylaminoazo dyestuif is then reduced to the meta-aminobenzoylaminoazo dyestuff and the latter is converted into the urea compound having in its free state the following formula 1. Azodyestufi's of the probable general formula:

wherein X represents a sulfur or oxygen atom, u and '0 represent residues of any desired coupling components, :1 and 2 stand for at least once a group of the kind -NH-Ra-, whereby R represents an aromatic nucleus and a represents one of the groups CO and S0 being linked to a nitrogen atom, said dyestuffs being yellow to coon on 00in CO-NHON=N H018 soln COOH HQaS

OH OCzHI COOH t NH H0:

NH OOOH black powders, sparingly soluble in the usual organic solvents, soluble in concentrated sulfuric acid with yellow to blue colorations, yielding on treatment with stannous chloride and hydrochloric acid among other products 2'.5-diaminobenzene-l-carboxylic acid.

2. Azodyestuifs of the probable general formula:

coon NHON=N-z on nncocm OH NH.O0.0H:

In this manner, a dyestufi is obtained which wherein X stands for a sulfur or oxygen dyesunmordanted cotton a reddish violet, atom, the two zs represent residues of any which on after-treatment with copper salts desired azocomponents and the two ys stand changes to a clear violet. for the group -NH-RCO, whereby R I claim: means an aromatic nucleus, said dyestuffs being yellow to black powders, sparing soluble in the usual organic solvents, soluble in concentrated sulfuric acid with yellow to blue colorations, yielding on treatment with stannous chloride and hydrochloric acid among other products 2.5 diaminobenzene 1 carboxylic acid.

3. Azodyestuffs of the probable general wherein X stands fora sulfuror oxygen atom, the twoizs represent residues of any desired coupling components containing sulfogroups, the two ys stand for the group -NHRCO, whereby R represents a benzene nucleus, said dyestufis being yellow to black powders, sparingly soluble in the usual organic solvents, soluble in concentrated sulfuric acid with yellow to blue colorations, yielding on treatment with stannous chloride and hydrochloric acid among other products 2.5 diaminobenzene 1 carboxylic acid and an aminobenzoic acid.

4. Azodyestuifs of the probable general formula:

wherein the two zs represent. residues of any desired azocomponents containingsulfogroups, said dyestuffs being yellow to black powders, sparingly soluble in the usual oranic solvents, soluble in concentrated suluric acid with yellow to blue colorations, yielding on treatment with stannous chloride and hydrochloric acid among other products 2.5-diamino-benzene-l-carboxylic acid and 3- aminobenzene-l-carboxylic acid. 7

5. The disazodyestuif havingin its free form the probable formula:

said dyestuif being in form of its sodium- RICHARD STUSSER. 

